Plant growth regulating composition

ABSTRACT

The present invention relates to a novel plant growth regulating composition which is characterized in that it contains as active ingredient one or more of quaternary ammonium halide having the formula, WHEREIN R is R1 is methyl, ethyl or allyl group, R2 and R3 are both methyl or bonded to each other to form -(CH2)4-, and X is chlorine or bromine atom. The quaternary ammonium halide have such specific biological activities on plants that plants are controlled in growth and continue to grow to effect an increase of fruit-bearing ratio, prevention of Jonathan spot or Jonathan freckle on apple fruit, improvement of fruit qualities after harvest and the like.

Unite r;

Tsnchiya et al.

ta att [1 1 Dec. 24, 119741- PLANT GROWTH REGULATING COMPOSTTION [75] Inventors: ll'lideshi Tsuchiya, Tokyo; Tetsuo Takematsu, Utsunomiya; Yoichi Hasegawa, Niigata; Masakazu Furushima, Matsudo, all of Japan [73] Assignee: Mitsubishi Gas Chemical Company, lnc., Tokyo, Japan 22 Filed: Apr.11, 1972 21 Appl.No.:243,058

[30] Foreign Application Priority Data Apr. 15, 1971 Japan 4623431 [52] US. Cl 260501.13, 71/95, 71/113, 260/326.42 [51] lnt. CL... C07c 103/30, C07c103/70,C07d 27/04 [58] Field oi Search 260/534 R, 501.13, 326.42; 71/45, 113

[56] References Cited UNITED STATES PATENTS 3/1966 l-lagemann et al. 260/534 E 7/1969 Hagemann et al. 260/534 E Primary Examiner-Vivian Garner Attorney, Agent, or FirmArmstrong, Nikaido & Wegner [57] ABSTRACT The present invention relates to a novel plant growth regulating composition which is characterized in that it contains as active ingredient one or more of quaternary ammonium halide having the formula,

wherein R is CH -CONH or CHCON'H-,

CH -COOH HOOGHC R is methyl, ethyl or allyl group, R and R are both methyl or bonded to each other to form -(CH and X is chlorine or bromine atom.

3 Claims, No Drawings thermore, the present compositions have actions to in- 'll PLANT GROWTH REGULATING COMPOSITION This invention relates to novel plant growth regulating compositions containing as active ingredient one or more of new compounds represented by the general formula, R

R is methyl, ethyl or allyl group, R and R are both methyl groups or may bond to each other to form (CH2)4- and X is a chlorine or bromine atom. The

compositions of the present invention are used for such various purposes as the increase in fruit-bearing ratio, the prevention of degradation in quality of fruits, the prevention of physiological diseases of apple, the prevention of cold and drought damages of plants, the obtainment of excellent ornamental garden flowers, etc.

Plant growth regulating chemicals have such actions as to promote or control the functions of plants which bring about such physiological phenomena as germination, root-taking, elongation, flower and differenti- 3O ation, flowering, fructification and fruit-falling. Recently, therefore, many attempts have been made to carry outwith advantages the cultivation of plants by use of such chemicals as mentioned above. For example, there have been made attempts to increase cold resistance, drought resistance and disease resistance to plants or to make leaf colors and fruit colors favorable by use of chemicals having actions to regulate the growth of plants. These chemicals,.however, have such drawbacks that in case the chemicals are used at somewhat high concentrations or are mixed with other chemicals, they not only tend to cause phytotoxicity but also deteriorate the taste of fruits and inhibit the thickening of fruits.

The compositions of the present invention have actions to regulate the growth of plants. In the cultivation of fruit trees, therefore, they can be used for the purpose of making the trees smaller to facilitate the pomicultural operation or to increase the yield of crops. Furhibit the useless growth of plants to make the plants grow strongly, so that they can be used for such purposes as the prevention of cold or drought damage of plants, the prevention of falling of fruits, the increases in number of flower buds, the promotion of coloration of fruits, and the prevention of Jonathan spot or Jonathan freckle which is physiological disease of apple. When the present compositions are applied to ornamental garden plants, it is possible to obtain excellent ornamental plants which have been shortened in leaf internode without any deformity of leaves and flowers. For example, when the present compositions are applied to chrysanthemu'ms, it is possible to obtain excellent ornamental ones. In case the seedlings of cucumber (Cucumis salivus L.) are cultivated in a greenhouse in winter, the seedlings sometimes grow uselessly to become weak due to insufficient sunlight. However, when the seedlings are treated with the present compositions, they can be made short in leaf internode and made strong even in a greenhouse in winter. It is also possible to spray the present compositions to fruit trees in order to save the operation of pruning. Further, the present compsitions have such characteristic that they do not cause any phytotoxicity even when applied to plants which have been sprayed with a bordeaux mixture.

The compound used as active ingredient of the present composition is soluble in water, alcohols, dimethylformamide, or the like, and hence is ordinarily used in such a manner that the compound is dissolved in water, and the resulting solution is incorporated with a surface active agent and then sprayed to plants so as to sufficiently wet the leaves, stems and fruits thereof, or in such a manner that seeds of plants are immersed in an aqueous solution of the present compound and the thus treated seeds are sowed.

In pomiculture, a 500 to 10,000 ppm. solution of the present compound is sprayed to fruit trees 1 to 2 times during a period between 30 days before flowering and days after flowering. To apple trees, for exam ple, a 500 to 2,000 ppm, aqueous solution of the present compound is sprayed l to 2 times during May to July. To grape vines, a 0.2 to 1.0% aqueous solution of the present compound is sprayed l to 2 times during May to June. In the culture of flowering plants or vegetables, a solution of the present compound at a concentration of about 0.2 to 0.85 is sprayed to the seedlings thereof so as to sufficiently wet the seedlings, or seeds of said plants or vegetables are immersed in said solution and are then sowed.

The compounds used as active ingredients of the' present plant growth regulating compositions are as shown in Table 1, though these are not limitative.

Table l gg f 7 Formula m.p.

f (in 7 l CH-CONH-N -cH c1 l36l38 C.

- CHZ-GOOH CH3 2 CHZ-CONH-NQ-CHB Br -143 0.

| (decomposition) OH2-OOOH 0H The compounds which are active ingredients of the present plant growth regulating compositions can be easily synthesized by reacted amidic acids with halogenated alkyls as shown in the following examples:

EXAMPLE 1 Synthesis of the compound 1: To a solution of g. (0.125 mole) of N- (dimethylamino) succinamic acid in ethanol was added 21.4 g. (0.15 mole) of methyl iodide, and the resulting mixture was refluxed for 2 hours. After completion of the reaction, excess methyl iodide and the ethanol were removed from the reaction product by means of evaporation to obtain 36.5 g. of a syrup-like substance. This substance was dissolved in a saturated aqueous solution of 17 g. (0.0625 mole) of mercuric chloride to precipitate a red mercuric iodide. The precipitate was removed by filtration, and the water in the filtrate was removed by means of evaporation. Subsequently, the residue was recrystallized from acetone to obtain 25.8 g. ofcrystals.

EXAMPLE 2 Synthesis of'the compound 2:

A mixture comprising 3.2 g. of N-(dimethylamino) succinamic acid of 6.05 g. of methyl bromide and methanol was tightly sealed in an autoclave and reacted at 60C. for 11 hours. Thereafter, the reaction liquid was taken out of the autoclave, and the methanol and excess methyl bromide were removed by distillation. The residue obtained was washed with a mixture of acetone and a small amount of methanol to obtain 2.0 g. of a white solid, m.p. l40-l43C., purity 98.2 as measured by titration.

EXAMPLE 3 Synthesis of the compound 21: A mixture comprising 5.6 g. of N-(l-pyrrolidyl) fumaramic acid, 5.2 g. of ethyl iodide and 50 cc. of methanol was refluxed for 15 hours. Subsequently, the

l6l-l63 C. (decomposition) methanol and excess ethyl iodide were removed by distillation to obtain 9.7 g. of a pale brown oily residue. This residue was dissolved in water, and the resulting solution was charged with an aqueous solution containing 4.1 g. of mercuric chloride to deposit a red precipitate of mercuric iodide. The precipitate was removed by filtration, and then hybrogen sulfide was introduced into the filtrate to precipitate the residual mercuric ion as a mercuric sulfide. This precipitate was removed by filtration, and the water in the filtrate was removed by distillation under reduced pressure, whereby about 7.4 g. of an oily substance was obtained. Subsequently, the oily substance was washed with acetone and then with a small amount of methanol to obtain 2.7 g. of a white powder, m.p. 161-165C., purity of about as measured by titration.

Procedures for preparation of the present compositionsand effects thereof are shown below with reference to examples.

EXAMPLE 4 Synthesis of the compound 24: A mixture comprising 1.8 g. of N-(l-pyrrolidyl) fumaramic acid iHCONH-NG HOOCHC 1.2 g. (0.01 mole) of allyl bromide and 20 ml of acetonitrile was refluxed for 3 hours. Subsequently, the acetonitrile was removed by distillation. The residue was recrystallized from acetone to obtain 2.5 g. of a white crystal, m.p. 16ll63C decomposed, purity 97 as measured by titration.

EXAMPLE 5 Test areas were provided on individual main branches of one apple tree (Malus pumila Miller). On the other hand. each of the compound 19 and l of the present invention was formed respectively into an aqueous solution of a given concentration, and the solution was incorporated with a spreader. The aqueous solution was sprayed to the test areas by means of a semi-automatic sprayer so as to sufficiently wet the leaves and fruits of the apple tree. Thereafter, each length of the shoots was measured. The results ob- EXAMPLE 7 tained were as shown in Table 2. Test areas were provided on individual main Table 2 Concen- At the time of At the time of Elon- Elon- Variety tration spraying measurement gation gallon (p.p.m.) Date Length Date Length (cm) ratio (cm) (cm) STAR 1,000 June 30 25.3 Sept. 46.2 20.9 44.1 Compound 19 KING 1,500 do. 28.6 do. 47.0 18.4 39.0 Control do. 30.5 do. 779 47.4 100.0 Compound l JONA- 1,000 July 20 15.5 Oct. 24.9 9.4 55.0

THAN Control do. l5.l do. 32.3 17.2 100.0

The apple tree treated with the present composition was less in number of uselessly elongated branches, and the shape thereof was markedly favorable from the standpoint of apple tree cultivation as shown in the following examples wherein the spreader having the folbranches of one apple tree. Subsequently, each of aqueous solutions of the present compounds 19 and 1 at given concentrations was sprayed to the test areas by means of a semi-automatic sprayer, so as to sufficiently wet the leaves and fruits of the apple tree. Falling ratios lowing composition was used. 20 of the fruits before harvest were as shown in Table 41.

Spreader: Table 4 Alkylaryl polyglycol ether 20.0271 Day of Concen Falling Sodium dinaphthylmethanesulfonate 6.0 Variety spraying nation ratio Organic solvent 74.0 71 25 (ppm) (7:)

EXAMPLE 6 June 1.000 5.3 Compound 19 STARKING do. 1.500 3.9 Test areas were provided on individual main Nonmatmem 3' branches of one apple tree (variety: JONATHAN). On Compmmd l film; My 20 O July 20, a 0.1 aqueous solution of the present com- 30 Non-treatment pound 1 which had been incorporated with a wetting EXAMPLE 8 agent was sprayed to the test areas by means of a semiautomatic sprayer so as to sufficiently wet the leaves and fruits of the apple tree. Thereafter, the extent of damages of each area due to Jonathan spot and Jonathan freckle was investigated. The results obtained were as shown in Table 3.

Table 5 Time of Concen- Hardness* Saccha** Acidity*** investigation Test area Variety tration rinity() (p.p.m.) (lbs) (cc) At the time Compound 1 JONA- 1,000 13.7 13.7 11.5

THAN

of harvest (Oct. 10) Non-treatment do. 13.0 13.4 11.4 th Day Compound 1 do. 1,000 13.1 13.7 11.4 after harvest Non-treatment do. 11.2 13.4 7.6

Compound 19 STARKlNG 1.000 16.1 14.0 11.2 At the time of harvest do. do. 1.500 16.9 13.4 11.3 (Oct. 15) Non-treatment do. 14.5 14.5 11.1 30th Day Compound 19 do. 1,000 10.4 14.2 11.0 after do. do. 1,500 -1 1.0 13.6 11.1 harvest Non-treatment do. 7.8 14.6 7.2

' Hardness: Mugnes-Tuylor pressure tester. with a 7/16 inch tip 1111s.). Succhurinily: Indication of refracrometer. Acidity: Amount of one-tenth N NaOH required [or neutralizing 10 cc ofjuicc.

Note: Damages (Z were calculated by (Damaged number of fruits/Total number of fruits in respective area X On the 60th day after the harvest, the apple fruits were sampled. As the result, the apple fruits from the control area were extremely inferior in taste. whereas 0 the apple fruits from the areas treated'with each of the present compounds 1 and 19 were as excellent in taste as those at the time of harvest.

EXAMPLE 9 Each of the present compounds 3 and 9 was formed into a given concentration aqueous solution, which was then incorporated with a wetting agent. Subsequently, the solution was sprayed to the shoots of grape vines (variety: KYOHO) so as to sufficiently wet the shoots.

Two weeks after the spraying, the lengths of the shoots were measured. The results obtained were as shown in Table 6.

EXAMPLE 11 Seeds of Black valentine bean (Phaseolus vulgaris L) Table 6 were immersed in an aqueous solution of the present compound 9 which had been incorporated with a ength Day f Come". Length r [gl Ekmga. spreader. After 10 hours, the seeds were taken out, suf- Tefit p yb95991 lion ficiently washed with water and then sowed in a soil. l2

. WCC'S ma mg (7') "cab from branch Days after the sowmg, the he ght of each seedlmg was ment trcat- (cm) (7r) measured and the phytotox1c1ty of the compound was (cm) 10 investigated. The results obtained were as shown in Table 8. As is clear from Table 8, it was confirmed that Com- June 7 1 90 133 43 5 even in the case of seed treatment, the present comg 05 87 m 72 pound displays its plant regulating effect and has no NOnphytotoxicity. lrcat- 89 I64 75 I00 ment C6m- June 1 1 85 121 36 49 pound Table 8 9 0.5 90 137 47 64 Non- Compound Concentranon Helght Elongauon Phyto- T 81 154 73 00 No. (p.p.m.) (cm) ratio (71) toxicity mcnt 2,000 4. N The grape vmes sprayed w1th the present compos1- 9 L000 70 39 l tions did not show any useless elongation of shoots, did 500 53 Non 18.0 100 do. not requ1re prumng, and had shapes qu1te favorable mama, from the standpoint of viticulture. 25

EXAMPLE l0 l0 Seeds of Black valentine bean (Phaseolus Vulgaris EXAMPLE 12 L) were sowed in a vat of 800 cm at 27C. When the primary leaves were partially expanded (3.5-5 cm Test areas were provided on individual main across) and the tr1fol1olate leaves were still folded in 30 branches of grape vines (variety: KYOHO). On the the term1nal bud, each of aqueous solutions of the preS- other hand, each of the present compounds 2, 9 and 21 ent compounds 7, 8, 9 and 19 wh1ch had been 1ncorp0- was formed into a given concentration solution. On rated w1th a spreader was uniformly sprayed to the May 21st, the solution was sprayed by means of a seedlings. 7 Days after the spraying, the length from the small size manual sprayer to the reverse sides of the second node to the tip of bud was measured and the leaves. On July 7, the lengths of shoots and the number phytotoxicities of the compounds were investigated. of berries per cluster were counted. The results ob- The results obtained were as shown in Table 7. tained were as set forth in Table 9. In all the test areas The compos1t1ons of the present invention had no to which the present compositions had been applied, phytotoxicity at all on the seedlings. the grape vines did not differ in time of flowering and Table 9 Compound Concent- Length of shoots (cm) Berries No. ration At the time On July 7 Elong- Ratio of Number of Ratio ('71) of treatment ation length berries (7() (7() per cluster 0.5 20.5 89.0 69.5 86 30.3 159 Nontreatment 20.0 101.0 81.0 19.0 100 Table 7 in number of leaves, were inhibited in elongation of Compound Come Elongation Elongmion Phyw shoots, and were Increased 1n number of berrtes.

No. rat'on (cm) atio (7) toxicit .i, y EXAMPLE 13 l 1,0 25 None In a flower pot were planted 3 chrystanthemum 35 60 plants (var. Bright Golden Princess Anne.) 14 Days 7 0.25 2.4 60 do. f h l (H25 3" 78 a ter t e p antat1on, leaf buds of the p ants were 1 2.5 63 d0. pinched off, and each of given concentration chemicals 8 8g 3g of the present compounds shown in Table 10 was Q5 I 1 23 sprayed to the plants. 70 Days after the spraying inves- 9 gzg i; g: 65 tigation was made with respect to the elongation state 20 of stem, the flowering time, the size of flower and the L1 28 shape of flowering plant. The elongation state of stem 19 0.25 1.9 48 do.

M25 21 53 m was as shown 1n Table 10.

Non- In each of the present chem1cal-treated plants. the

lrcatmcnt 4.0 I00 do.

length of stem was about 2 to 10 cm. shorter than in the Table 11 Compound Concent- Height at the Height after Elongation Ratio of elon- Phytoration time of 40 days during 40 gation to that No. treatment (cm) days (cm) in non-treatcd toxicity (cm) area (cm) 0.5 16.7 26.9 10.2 64 NOHC 2 0.25 16.7 31.0 14.3 89 dd. 0.5 16.3 24.8 8.5 53 d6. 19

0.25 15.9 25.3 9.4 59 d6. 0.5 16.5 24.0 7.5 47 do. 21

0.25 16.3 25.0 8.7 54 dd. 0.5 16.6 28.8 12.2 76 do. 24

0.25 16.2 31 14 8 92 d6. Nontreatment 16.3 32.3 16.0 100 do.

Table 25 A bordeaux mixture (copper sulfate quick lime water was 1 2 320 by weight) was sprayed to seed- Compound Concentration Len h of m (cm) 1 lings of cucumber (Cucumis sativus L). On the next No. ("/21 At the time 70 Days after day, 0.5 aqueous solution of the present compound 211 was sprayed thereto. After 2 weeks, investigation 08 6'5 200 was made with respect to phytotoxicity to find that the 1 present composition showed no phytotoxicity even when applied quickly after spraying of the bordeaux 4 mixture. Of course, no phytotoxicity was observed in 0.4 6.5 24.0 the non-treated plants, which had been sprayed only 5 640 v 5; with the bordeaux mixture. 7

0.4 6.0 22.3 0.8 6.5 19.0 7 EXAMPLE 1 Effects of the present compounds on poinsettias (Eu- 12 6 phorbia pulcherrima WILLDENOW):

0.8 6.5 16.0 13. Pomsettla plants (red), wh1ch had grown to about 15 8'; 2'3 :38 -cm., were transplanted in pots in a proportion of 3 I6 plants per pot. 3 Days after the transplantation, each of 0.4 6.5 24.0 given concentration aqueous solutions of the present 8 compounds shown in Table 11 was sprayed by means 1 0.4 6D 2L0 of a microsprayer onto the surfaces of leaves of the Q8 140 plants. 40 Days after the spraying, the height of each 21 plant was measured. The results obtained were as g"; 2': 53'? shown in Table 11. The treated plants were lower in 24 height than those in the non-treated plants, and were 0.4 6.5 24.0 55 suitable for ornamental potted plants. Nonv treatment 6.5 27.5

We claim: l. A quaternary ammonium halide having the for- EXAMPLE .14 mula,

non-treated plantpand the flowering time, and the size, color and shape of flower did not differ from those in I the non-treated area. As to the shape of flowering R N R X plant, however, the plants in the non-treated area were I great in height and were not suitable for ornamental R purposes. 3

15 16 whe e n R S I claim 1, wherein R is CH CONH CH -CONH OI CHCONH, R

CH COOH CH COOH HOOCHC 5 3. A quaternary ammonium halide according to claim 1, wherein R is R methyl, ethyl or allyl group, R and R are both methyl or bonded to each other to form (CH F and X is chlorine or bromine atom. 10 HOOCHC 2. A quaternary ammonium halide according to 

1. A QUATERNARY AMMONIUM HALIDE HAVING THE FORMULA
 2. A quaternary ammonium halide according to claim 1, wherein R is
 3. A quaternary ammonium halide according to claim 1, wherein R is 